CN1293653C - A total solid state lithium micro cell positive electrode film and method for making same - Google Patents

A total solid state lithium micro cell positive electrode film and method for making same Download PDF

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Publication number
CN1293653C
CN1293653C CNB2005100183573A CN200510018357A CN1293653C CN 1293653 C CN1293653 C CN 1293653C CN B2005100183573 A CNB2005100183573 A CN B2005100183573A CN 200510018357 A CN200510018357 A CN 200510018357A CN 1293653 C CN1293653 C CN 1293653C
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thin film
film
preparation
micro cell
lini
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CN1655381A (en
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刘韩星
朱先军
甘小燕
胡晨
曹明贺
罗大兵
欧阳世翕
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention discloses a preparation method of a thin film of the positive electrode of a full solid lithium microbattery LiNi [1-x]Co [x]O2. The thin film of the positive electrode is prepared by that acetylacetone lithium or acetylacetone nickel and cobalt acetate are used as raw materials, the raw materials are exactly weighed according to the molar ratio of the prepared LiNi [1-x]Co [x]O2 to Co and the molar ratio of Li to (Ni+Co), and the molar ratio of Li to (Ni+Co) is 1.00 to 1.05:1.00; the raw materials are dissolved in mixed solvent in which the molar ratio of acetic acid to alcohol is 1:1, and collosol is prepared. A thin film of gelation is prepared on a basal body with Pt surfaces and Au surfaces by an even glue method is used, the thin film is preheated and decomposed at temperature of 350 to 400 DEG C, anneal is carried out in oxygen atmospere at temperature of 650 to 750 DEG C, and the thin film of the positive electrode is prepared, wherein x is smaller than or equal to 0 and is larger than or equal to 1.0. The thin film preparation method provided by the present invention has simple technology and apparatus, and is easy to prepare a thin film of a positive electrode, and the thin film has large areas.

Description

The total solid state lithium micro cell positive electrode film preparation method
Technical field
The invention discloses a kind of total solid state lithium micro cell LiNi 1-xCo xO 2The preparation method of anode thin film.It belongs to electrochemistry and electronics applications technical field.
Background technology
Total solid state lithium micro cell is the novel micro cell that grew up in recent years, its reason is with seeing that microelectronic component, dynamic random holder, microsensor, micro-electromechanical system, the systems such as medical device that implant develop towards the ultraminiaturization direction, no longer to pursue power and electric current, an urgent demand has the micro power that volume is little, in light weight, specific capacity is high to be complementary with it to the requirement of power supply.The full solid thin film lithium micro cell has the mechanical strength height, does not contain inflammable and volatile component, does not have safety problems such as leakage, and the storage life of this class battery with overlength, is fit to do the Power Support of all kinds of microelectronic products.Full solid thin film lithium micro cell performance is subjected to the anode film material Effect on Performance bigger, and anode film material is generally transition metal oxide, and obtains inexpensively, and high performance composite oxide positive pole material film is the key of development full solid thin film lithium micro cell.At present, the preparation method of positive electrode film mainly contains radio-frequency magnetron sputter method, pulsed laser deposition, chemical vapor deposition (CVD) method etc.In these system membrane meanses, relate to expensive instrument and equipment, system film cost height, perhaps filming technology complexity, it is good etc. to make film performance.
Summary of the invention
The objective of the invention is to LiNi 1-xCo xO 2Material is used for full solid thin film lithium micro cell anode thin film, and a kind of preparation full solid thin film lithium micro cell LiNi is provided 1-xCo xO 2The method of anode thin film.This method has been avoided anode thin film preparation cost height in the at present relevant patent documentation, and complex process makes shortcomings such as the performance of film is not good, and anode thin film preparation technology is simplified greatly; The anode thin film densification of preparation, and have better electrochemical performance; Can make the larger area film.
The object of the present invention is achieved like this:
Full solid thin film lithium micro cell anode film material of the present invention is LiNi 1-xCo xO 2, the value of x is 0≤x＜1.0.
The said full solid thin film lithium micro cell preparation method of anode thin film: with the acetylacetone,2,4-pentanedione lithium, nickel acetylacetonate, cobalt acetate are raw material, by prepared LiNi 1-xCo xO 2, the mol ratio of Li, Ni, Co is Li/ (Ni+Co)=1.00～1.05 in 0≤x＜1.0: 1.00 accurate each raw material of weighing, the mol ratio that is dissolved in acetic acid and alcohols are to make colloidal sol in 1: 1 the mixed solvent; Sol coating is made gel film on the matrix with Pt or Au surface, gained gel film evaporating solvent and the organic salt of Li, Ni and Co decomposed on 350～400 ℃ hot plate is made sull.Sull is placed high temperature sintering furnace, and under oxygen atmosphere, 650～750 ℃ of annealing 10～60min promptly get and have α-NaFeO 2The LiNi of layer structure 1-xCo xO 2Film.Make film thickness as required, " even glue → heating → annealing " process can be repeated repeatedly, till the film thickness that requires.
The method that said sol coating adopts is even glue method (spin coating).。
Said alcohols comprises: methyl alcohol, ethanol, propyl alcohol, butanols, 2-methoxyl group ethylene glycol, and two kinds and two or more mixed alcohols of described alcohol.
After tested, the LiNi that makes 1-xCo xO 2Film compactness is good, even and have a better electrochemical performance.Between 4.15～3.50V, can be used for total solid state lithium micro cell positive electrode film with respect to the discharge potential of lithium reference electrode.
Compared with the prior art, the LiNi of the present invention's preparation 1-xCo xO 2Anode thin film has following distinguishing feature:
The LiNi of 1 preparation 1-xCo xO 2Film densification, even has α-NaFeO 2Layer structure
The specific capacity height of 2 films, good cycle
3 can make thicker, larger area film
4 technologies, equipment are simple, are easy to grasp, and cost is low
The invention will be further described below in conjunction with example:
Embodiment
Embodiment 1:
LiNi 0.80Co 0.20O 2Film preparation: accurately take by weighing Li (CH 3COCH 2COCH 2) 0.5817g, Ni (CH 3COCH 2COCH 2) 24H 2O 1.2722g, Co (CH 3COO) 24H 2O 0.2705g dissolves in the mixed solvent of the 10ml tert-butyl alcohol and 6.1ml acetic acid, makes colloidal sol after the dissolving fully.The method of the even glue of employing on the Pt matrix through polishing, polishing, makes gel film with prepared sol coating.Even glue rotating speed is 3000 rev/mins, and the even glue time is 30 seconds.The gained gel film is heated 5min in 400 ℃ of temperature on hot plate, make solvent evaporation, and the organic salt of Li, Ni, Co is resolved into sull.Sull is placed high temperature sintering furnace, and under oxygen atmosphere, 700 ℃ of annealing temperatures 60 minutes promptly get and have α-NaFeO 2The LiNi of layer structure 0.80Co 0.20O 2Film.Repeat " even glue → heating → annealing " process 9 times, the thickness of gained film is 0.5 μ m after tested.At 50 μ A/cm 2In electric current, the 3.0～4.2V voltage range, be 1mol/l LiClO with concentration 4/ EC+DMC (1: 1 volume ratio of ethylene carbonate+carbonic acid two Party A's esters) is an electrolyte, is the lithium sheet to electrode, prepared LiNi 0.80Co 0.20O 2Film discharge capacity first reaches 58.4 μ Ah/cm 2μ m, after 50 circulations, discharge capacity is 45.6 μ Ah/cm 2μ m shows its excellent cycle performance.
Embodiment 2:
LiNiO 2Film preparation: accurately take by weighing Li (CH 3COCH 2COCH 2) 0.5817g, Ni (CH 3COCH 2COCH 2) 24H 2O 1.5903g dissolves in the mixed solvent of the 10ml tert-butyl alcohol and 6.1ml acetic acid, makes colloidal sol after the dissolving fully.The method of the even glue of employing on the Pt matrix through polishing, polishing, makes gel film with prepared sol coating.Even glue rotating speed is 3000 rev/mins, and the even glue time is 30 seconds.The gained gel film is heated 5min in 380 ℃ of temperature on hot plate, make solvent evaporation, and the organic salt of Li, Ni, Co is resolved into sull.Sull is placed high temperature sintering furnace, and under oxygen atmosphere, 750 ℃ of annealing temperatures 60 minutes promptly get and have α-NaFeO 2The LiNiO of layer structure 2Film.Repeat " even glue → heating → annealing " process 9 times, the thickness of gained film is 0.5 μ m after tested.At 50 μ A/cm 2In electric current, the 3.0～4.2V voltage range, with 1M LiClO 4/ EC+DMC (1: 1 volume ratio) is an electrolyte, is the lithium sheet to electrode, prepared LiNiO 2Film discharge capacity first reaches 49.4 μ Ah/cm 2μ m, after 50 circulations, discharge capacity is 30.5 μ Ah/cm 2μ m.

Claims (3)

1, a kind of full solid thin film lithium micro cell preparation method of anode thin film, this thin-film material is LiNi 1-xCo xO 2, the value of x is 0≤x＜1.0, it is characterized in that preparation process is:
Step 1, with the acetylacetone,2,4-pentanedione lithium, nickel acetylacetonate, cobalt acetate are raw material, by prepared LiNi 1-xCo xO 2, the mol ratio of Li, Ni, Co is Li/ (Ni+Co)=1.00～1.05 in 0≤x＜1.0: 1.00 accurate each raw material of weighing, the mol ratio that is dissolved in acetic acid and alcohols are to make colloidal sol in 1: 1 the mixed solvent;
Step 2, the sol coating that step 1 is made make gel film on the matrix with Pt or Au surface, through 350～400 ℃ of predecomposition, the 10～60min that anneals in 650～750 ℃ of temperature oxygen atmospheres more promptly gets one deck LiNi 1-xCo xO 2Film;
Even glue → heating → annealing the preparation process of step 3, repeating step 2 is till required film thickness.
2,, it is characterized in that the method that said sol coating adopts is even glue method by the preparation method of the said full solid thin film lithium micro cell of claim 1 with anode thin film.
3, by the preparation method of the said full solid thin film lithium micro cell of claim 1, it is characterized in that said alcohols comprises: methyl alcohol, ethanol, propyl alcohol, butanols, 2-methoxyl group ethylene glycol, and two kinds and two or more mixed alcohols of described alcohol with anode thin film.
CNB2005100183573A 2005-03-09 2005-03-09 A total solid state lithium micro cell positive electrode film and method for making same Expired - Fee Related CN1293653C (en)

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CN101640265B (en) * 2009-07-13 2011-09-07 北京安华联合能源科技有限责任公司 Preparation method of LiFePO4 film lithium ion battery anode with dispersed nano-silver particles
CN102456926B (en) * 2010-10-28 2014-10-22 华东师范大学 Novel three-dimensional lithium ion battery construction method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5153081A (en) * 1989-07-28 1992-10-06 Csir Lithium manganese oxide compound
CN1289738A (en) * 1999-09-27 2001-04-04 北京有色金属研究总院 Process for preparing positive electrode material of Li-ion battery
AU2002100000A4 (en) * 2002-01-02 2002-03-07 Dou, Shi Xue Cathode materials for rechargeable lithium batteries and a process for production
CN1567620A (en) * 2003-06-25 2005-01-19 南都瑞宝能源科技（上海）有限公司 Anode material--lithium nickelate cobalt for lithium ion battery and preparation method thereof
CN1571188A (en) * 2003-07-25 2005-01-26 桂林工学院 Phase transition synthesizing method for doping lithium manganate powder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5153081A (en) * 1989-07-28 1992-10-06 Csir Lithium manganese oxide compound
CN1289738A (en) * 1999-09-27 2001-04-04 北京有色金属研究总院 Process for preparing positive electrode material of Li-ion battery
AU2002100000A4 (en) * 2002-01-02 2002-03-07 Dou, Shi Xue Cathode materials for rechargeable lithium batteries and a process for production
CN1567620A (en) * 2003-06-25 2005-01-19 南都瑞宝能源科技（上海）有限公司 Anode material--lithium nickelate cobalt for lithium ion battery and preparation method thereof
CN1571188A (en) * 2003-07-25 2005-01-26 桂林工学院 Phase transition synthesizing method for doping lithium manganate powder

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